WO2004069975A1

WO2004069975A1 - Increase in the water absorption capacity of textiles

Info

Publication number: WO2004069975A1
Application number: PCT/EP2004/000872
Authority: WO
Inventors: Josef Penninger
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2003-02-10
Filing date: 2004-01-31
Publication date: 2004-08-19
Also published as: EP1592764A1; EP1592764B1; ATE350447T1; JP2006517264A; ES2279344T3; US20060035806A1; JP4578465B2; DE502004002541D1

Abstract

The aim of the invention is to increase the water absorption capacity of synthetic textiles. This is achieved by using a cellulose derivative with dirt dissolving properties, obtained by the alkylation and hydroxyalkylation of cellulose.

Description

"Increasing the water absorption capacity of textiles"

The present patent application relates to the use of cellulose derivative which is capable of producing dirt and soils, in order to increase the water absorption capacity of textiles made of synthetic material.

When developing the present subject matter of the invention, it was assumed that textiles which are soiled when moist are often much easier to clean than those in which the soiling meets a completely dry textile. In order to achieve an improved washing result when washing soiled textiles, it is consequently desirable to have a textile which, at least on the surface, had a certain moisture content before it came into contact with the soiling. While textiles made of cotton or wool, for example, have a relatively high water absorption capacity and therefore easily reach a state of sufficient moisture, textiles made of synthetic material are normally only capable of extremely low water absorption. In order to achieve an improvement in the washing result using these effects, their water absorption capacity must consequently be increased.

Surprisingly, it has been found that the water absorption capacity of textiles made of synthetic material increases when they are washed in the presence of certain dirt-releasing ceululose derivatives.

The invention therefore relates to the use of cellulose derivative which is capable of producing dirt and is capable of being obtained by alkylation and hydroxylation of cellulose, in order to increase the water absorption capacity of textiles made of synthetic material. Preferred cellulose derivatives are those which are alkylated with ci to do groups, in particular ci to C ₃ groups, and additionally carry C ₂ to C _ϊ o-hydroxyalkyl groups, in particular C2 to C ₃ hydroxyalkyl groups. These can be obtained in a known manner by reacting cellulose with appropriate alkylating agents, for example alkyl halides or alkyl sulfates, and then reacting with corresponding alkylene oxides, for example ethylene oxide and / or propylene oxide. In a preferred embodiment of the invention, the cellulose derivative contains on average 0.5 to 2.5, in particular 1 to 2, alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3, hydroxyalkyl groups per anhydroglycosomer monomer unit. The average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 10,000 D to 150,000 D, in particular from 40,000 D to 120,000 D and particularly preferably in the range from 80,000 D to 110,000 D. The degree of polymerization or the molecular weight is determined of the dirt-releasing cellulose derivative is based on the determination of the intrinsic viscosity of sufficiently dilute aqueous solutions using an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H. Staudinger and F. Reinecke, "About molecular weight determination on cellulose ethers", Liebigs Annalen der Chemie 535, 47 (1938)] and a correction factor [F. Rodriguez and LAGoettler, "The Flow of Moderately Concentrated Polymer Solutions in Water", Transactions of the Society of Rheology VIII, 3 17 (1964)] can be used to calculate the degree of polymerization and the corresponding molecular weight, taking into account the degrees of substitution (DS and MS).

The use according to the invention is preferably carried out in the course of a washing and / or laundry post-treatment step in which the cellulose derivative which allows dirt to be removed is used. The invention therefore furthermore relates to a process for increasing the water absorption capacity of textiles made of synthetic material by washing and / or aftertreatment of the textile in the presence of dirt-free cellulose derivative which can be obtained by alkylation and hydroxyalkylation of cellulose.

As described, the cellulose derivatives used according to the invention can be produced in a simple manner and are ecologically and toxicologically harmless. They drove to one significantly higher water absorption capacity of textiles made of synthetic material, if they are treated with them, which leads to an improvement in the cleaning result, in particular the fat removal, during the next washing process and also during further washing processes of the textile treated in this way. Alternatively, significant amounts of surfactants can be saved while maintaining the ability to remove fat.

It is preferred if the textiles to be treated according to the invention consist of or contain polyester, polyamide, polyacrylonitrile, elastane or mixtures thereof. The latter variant means, for example, so-called cotton blends which contain cotton and synthetic material in the blended fabric.

The use according to the invention can take place in the context of a washing process in such a way that the cellulose derivative is added to a detergent-containing liquor or preferably the cellulose derivative is introduced into the liquor as part of a detergent.

The use according to the invention in the context of a laundry aftertreatment process can accordingly take place in such a way that the cellulose derivative is added separately to the washing liquor which is used after the washing step using a detergent, or as a component of the laundry aftertreatment agent, in particular a fabric softener. In this aspect of the invention, the said detergent can also contain a cellulose derivative to be used according to the invention, but it can also be free of this.

Agents which contain a cellulose derivative to be used according to the invention can contain all the usual other constituents of such agents which do not interact with the cellulose derivative in an undesirable manner. The cellulose derivative is preferably incorporated into detergent in amounts of 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight.

Surprisingly, it was found that the cellulose derivative used according to the invention has the effect of certain other detergent and cleaning agent contents. Substances positively influenced and that, conversely, the effect of the cellulose derivative used according to the invention is enhanced by certain other washing agent ingredients. These effects occur in particular in the case of enzymatic active substances, in particular proteases and lipases, in water-insoluble inorganic builders, in water-soluble inorganic and organic builders, in particular based on oxidized carbohydrates, in the case of peroxygen-based bleaching agents, in particular in the case of alkali percarbonate, in the case of synthetic anionic surfactants of the sulfate and sulfonate type and in Graying inhibitors, for example other, in particular anionic cellulose ethers such as carboxymethyl cellulose, and laundry softening agents, in particular ester quats, which is why the use of at least one of the further ingredients mentioned together with the combination to be used according to the invention is preferred.

In a preferred embodiment, such an agent contains nonionic surfactant, selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or Fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.

A further embodiment of such agents comprises the presence of synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount in the range from 2% by weight to 25% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.

The nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be known Be prepared by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. In addition, there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters, as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes in US Pat. No. 1,985,424. US 2 016 962 and US 2 703 798 and international patent application WO 92/06984 can be considered. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean. Such compounds and their preparation are described, for example, in European patent applications EP 92355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828. The glycoside component (G) _n is an oligomer or polymer from a naturally occurring aldose or ketose monomer, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, Include arabinose, xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of oligomerization. The degree of oligomerization n generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl part R ^{12 of} the glycosides preferably also comes from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although also whose branched chain isomers, in particular so-called oxo alcohols, can be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is contained in agents which contain a cellulose derivative used according to the invention, preferably in amounts of 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight, with amounts in the upper part thereof Range are more likely to be found in liquid detergents and particulate detergents preferably contain smaller amounts of up to 5% by weight.

Instead or in addition, the agents can contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, each based on the total mean. Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Such alkyl and / or alkenyl sulfates are in the compositions which contain a urethane-based polymer according to the invention, preferably in amounts from 0.1% by weight to 15% by weight, in particular from 0.5% by weight to Contain 10% by weight.

The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfomerization products, and the sulfofatty acids resulting from these by formal hydrolysis.

If desired, the agents can also contain betaines and / or cationic surfactants which - if present - are preferably used in amounts of 0.5% by weight to 7% by weight. Among them, the ester quats discussed below are particularly preferred.

Soaps can be considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable. In particular, those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C ₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid compositions which contain a cellulose derivative used according to the invention, higher amounts of soap, as a rule, of up to 20 wt.

In a further embodiment, an agent which contains a combination to be used according to the invention contains water-soluble and / or water-insoluble builders, in particular selected from alkali alumosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5% to 60% by weight.

An agent which contains a cellulose derivative to be used according to the invention preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarbonate acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of international patent application WO 93/16110 accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which are also minor Portions of polymerizable substances without carboxylic acid functionality can be copolymerized. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and StyroL, in which the proportion of acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C ₄ -carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2, are very particularly preferred. 5: 1 Both the amounts and the weight ratios are based on the acids. The second acidic monomer or the salt thereof can also be a derivative of an alkyl sulfonic acid which is substituted in 2-control with an alkyl group, preferably with a Cr alkyl group, or an aromatic group, which is preferably derived from benzene or benzene derivatives. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% by weight to 25% by weight of methyl sulfonic acid or methallyl sulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, OHgo- or polysaccharide, mono-, di- or OHgosaccharide are preferred, sucrose is particularly preferred. The use of the third monomer presumably incorporates break-in taxes in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers can be prepared in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 and 10,000. They can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Organic builder substances of this type are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

The water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali alumosicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions in particular from 1% by weight to 5% by weight. , used. Among these, the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit are preferably in solid, particle-shaped Funds used. Suitable aluminum silicates in particular have no tissues with a grain size of more than 30 mm and preferably consist of at least 80% by weight of tissues with a size of less than 10 mm. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, lies in the range from 100 to 200 mg CaO per gram. Suitable substitutes or tea substitutes for the alumosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the compositions preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or MstalHn. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ O: SiO ₂ molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portü®. Those with a molar Na ₂ O: SiO ₂ ratio of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427. They are preferably added as a solid and not in the form of a solution. Crystalline layered silicates of the formula Na ₂ Si _x θ2 _X + ₁ 'yH ₂ O, in which x, the so-called modulus, a number of 1, are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates , 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium disuicate (Na ₂ Si ₂ θ ₅ -yH ₂ O) are preferred, whereby β-sodium disuicate can be obtained, for example, by the process described in international patent application WO 91/08171. δ-sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Also practically water-free crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can be prepared from amorphous alkali silicates, as in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 425 428 described, can be used in agents containing a cellulose derivative used according to the invention. In a Another preferred embodiment of the agents uses a crystal sodium silicate layer with a modulus of 2 to 3, as can be made from sand and soda according to the process of European patent application EP 0436 835. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5, as obtained by the processes of European patent EP 0 164 552 and / or European patent application EP 0294753, are used in a further preferred embodiment of washing or cleaning agents , which contain a cellulose derivative used according to the invention. Their alkali silicate content is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali halide, in particular ZeoUth, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The Afumosüikat to Süikat weight ratio, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.

In addition to the inorganic builder mentioned, other water-soluble or water-insoluble inorganic substances can be used in the compositions which contain a Ceululose derivative to be used according to the invention. In this context, the alkali carbonates, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable. Such additional inorganic material can be present in amounts up to 70% by weight.

In addition, the agents can contain other ingredients that are customary in washing and cleaning agents. These optional Bestandteüen include, in particular enzymes, enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example A ninopolycarbonsäuren, Aminohydroxypolycarbonsäu- reindeer, polyphosphonic acids and / or aminopolyphosphonic acids, Farbfixierwirkstoffe, dye transfer inhibitors, for example PolyvinylpyrroHdon or Polyvinylpyrdin- N-oxide, foam inhibitors, for example organopolysiloxanes or Paraffins, solvents, and optical heaters, for example Stübendisulfonsäurederivate. In front- up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ', are preferably present in agents which contain a combination used according to the invention. -Bis (2,4,6-friarnino-s-tri-azinyl) -stüben-2,2'-disulfonic acid, up to 5% by weight, in particular 0.1% by weight to 2% by weight % Complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, up to 3% by weight, in particular 0.5% by weight to 2% by weight, of graying inhibitors and up to 2% by weight, in particular 0, Contain 1% by weight to 1% by weight of foam inhibitors, the weight percentages in each case referring to the entire average.

In addition to water, solvents which are used in particular in the case of liquid agents are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the compound classes mentioned. In such liquid compositions, the Ceululose derivative used according to the invention is usually present in solution or in suspended form.

Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicelfulase, oxidase, peroxidase or mixtures of these. Protease obtained from microorganisms such as bacteria or fungi is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 1940 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,623,957 and US 4,264,738, European patent application EP 006 638 and international patent application WO 91/02792. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase that can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacülus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384717. from Pseudomonas species, such as in European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international patent application WO 90/10695, from Fusarium- Species, as described for example in the European patent application EP 130 064, from Rhizopus species, as described for example in the European patent application EP 117 553, or from Aspergülus species, as described for example in the European patent application EP 167309. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The cellulase which can be used can be an enzyme which can be obtained from bacteria or puddles and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5. Such cellulases are known, for example, from German patent applications DE 31 17250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 and known from international patent applications WO 95/02675 and WO 97/14804 and commercially available under the names Ceüuzyme®, Carezyme® and Ecostone®.

The usual enzyme stabilizers which may be present, in particular in liquid agents, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, as known, for example, from European patent applications EP 376 705 and EP 378 261, Boric acid or alkali borates, boric acid-carboxylic acid combinations, as known, for example, from European patent application EP 451 921, boric acid esters, such as known from international patent application WO 93/11215 or European patent application EP 511 456, boronic acid derivatives, such as from European patent application EP 583 536 known, calcium salts, for example the Ca-formic acid combination known from European patent EP 28 865, magnesium salts, such as known from European patent application EP 378 262, and / or sulfur-containing reducing agents, such as from de European patent applications EP 080 748 or EP 080 223 are known. Suitable foam inhibitors include long-chain soaps, in particular beech soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances, such as, for example, in German Offenlegungsschrift DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386 described.

A further embodiment of such an agent, which contains a cellulose derivative to be used according to the invention, contains bleaching agents based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range of 2% by weight % to 10% by weight. These bleaches in question are the per compounds typically used in detergents, such as hydrogen peroxide, perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents which contain a cellulose derivative used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight on the entire medium, with percarbonate in particular being used. The optional component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tettacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluru, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfuryl amides, sulfuryl amides also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, especially pentaacetyl glucose, and cationic nitrile derivatives such as trimethyl-ammonium acetonitrile salts. The bleach activators can be coated or granulated in a known manner with shell substances in order to avoid the interaction with the per-compounds during storage, with the aid of carboxymethyl cellulose granulated tetraacetyl ethylenediamine with average grain sizes of 0.01 mm to 0.8 mm, as can be obtained, for example, by the process described in European Patent EP 37 026, gram-coated 1,5-diacetyl-2,4-dioxohexahydro-1,3. 5-triazine, as can be prepared by the process described in German Patent DD 255 884, and / or by the methods described in international patent applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or The process described in particle form of trialkylammonium acetonitrile described in WO 02/26927 is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.

It is also possible to use the so-called dirt-releasing ceululose derivative together with a polyester-active dirt-releasing polymer made from a dicarboxylic acid and a possibly polymeric diol to enhance the cleaning performance of detergents when washing textiles.

The known polyester-active dirt-releasing polymers which can be used in addition to the cellulose derivative essential to the invention include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. The preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR ^u -) _a OH, which is also used as a polymer Diol H- (O- (CHR ₁₁ -) _a ) bOH. Ph is an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{u is} hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures, a a number from 2 to 6 and b a number from 1 to 300. Preferably, both monomer diol units -O- (CHRπ-) aO- and polymer diol units - (O- (CHR ^u -) _a ) bO- before. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units the Degree of polymerization b preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight increase of preferred dirt-releasing polyester is in the range from 250 to 100,000, in particular from 500 to 50,000. The rest of the Ph the underlying acid is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, meüithic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among them, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small amounts, in particular not more than 10 mol%, based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ^π -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the latter diols, those of the formula HO-CH2-CHR ⁿ -OH, in which R ^{11 has} the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol and neopentyl glycol. Polyethylene glycol with an average poppy mass in the range from 1000 to 6000 is particularly preferred among the polymeric diols.

If desired, the polyesters composed as described above can also be end group-closed, alkyl groups with 1 to 22 C atoms and esters of monocarboxylic acids being suitable as end groups. The end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 C atoms, in particular 5 to 18 C atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, Undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, pam itic acid, stearic acid, petrosenic acid, petrosenergic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, elaostearic acid, arachic acid, brassachidonic acid, eradic acidic acid, gadoleic acid, eradic acidic acid, gadoleic acid, eradic acid acid, gadoleic acid, gadoleic acid, gadoleic acid, eradic acid, gadoleic acid , Lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxy monocarboxylic acids can in turn be linked to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units are Have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used together with the combination essential to the invention.

The dirt-releasing polymers are preferably water-soluble, the term “water-soluble” being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8. See preferred polymers under these conditions however, a solubility of at least 1 g per liter, in particular at least 10 g per liter.

Preferred laundry aftertreatment compositions which contain a Ceululose derivative to be used according to the invention have a so-called ester quat as the fabric softening active ingredient, that is to say a quaternized ester of carboxylic acid and amino alcohol. These are known substances that can be obtained using the relevant methods of preparative organic chemistry. In this connection, reference is made to the international patent application WO 91/01295, according to which triethanolarnine is used esterified in the presence of hypophosphorous acid with fatty acids, air passed through and then quaternized with dimethyl sulfate or ethylene oxide. German patent DE 43 08 794 also discloses a process for the production of solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols. Overviews on this topic are, for example, by RPuchta et al. in Tens.Surf.Det, 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J.Am.Oü.Chem.Soα, 71, 97 (1994) and I.Shap o in Cosm.Toü. 109, 77 (1994) appeared.

Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow the formula (I)

X (I)

in which R ^J CO stands for an acykest with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R * CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ θ) _q H- Group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C ₁₂ / ιs coconut fatty acids and in particular cost-hardened Ci6 / ₁₈ tallow or palm fatty acids and elaic acid-rich Ciö / is fatty acid cuts are preferably used. The fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the esterquats an operating ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical .Ci6 / ₁₈ - tallow or palm fatty acid (iodine number 0 to 40) , Quaternized fatty acid ethanol ammonium salts of the formula (I) in which R * CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ^x CO, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p for 0 and X for Methyl sulfate is particularly advantageous.

In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolaecylamines of the formula (II) are also suitable as ester quats,

R ⁴ rR ¹ CO- (OCH2CH2) _m OCH2CH2-N ⁺ -CH ₂ CH2θ- (CH ₂ CH2θ) _n R ² ] X (II)

in which R CO stands for an acyl residue with 6 to 22 carbon atoms, R ² for hydrogen or R ^ O, R ⁴ and R ⁵ independently of one another for alkyl residues with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

The quaternized ester salts of carboxylic acids with 1,2-dimydroxypropyl dialkylamines of the formula (DT) should also be mentioned as a further group of suitable ester quats:

R ⁶ O-CCHaCH _∑ O DCR ¹ [R ⁴ -N ⁺ -CH ₂ CHCH ₂ θ- (CH ₂ CH ₂ θ) _n R ² ] X ^" (DI)

in the R * CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R * CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the exemplary information given for (I) also applies analogously to the esterquats of the formulas (II) and (m). The esterquats usually come on the market in the form of 50 to 90 percent by weight alcoholic solutions, which can also be diluted with water without problems, ethanol, propanol and isopropanol being the usual alcoholic solvents.

Ester quats are preferably used in amounts of 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used according to the invention can additionally contain the laundry detergent ingredients listed above, provided that they do not unacceptably interact negatively with the esterquat. It is preferably a liquid, water-containing agent which is easily accessible by mixing the ingredients.

In a preferred embodiment, an agent into which a cellulose derivative to be used according to the invention is incorporated is tissue-like and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight .-%, in particular 1% by weight to 10% by weight of bleach activator, 20% by weight to 55% by weight of inorganic vapors, up to 10% by weight, in particular 2% by weight to 8% by weight. % water-soluble organic builder, 10% by weight to 25% by weight synthetic anionic surfactant, 1% by weight to 5% by weight nonionic surfactant and up to 25% by weight, in particular 0.1% by weight up to 25% by weight of inorganic salts, in particular alkali carbonate and / or hydrogen carbonate

In a further preferred embodiment, an agent into which a cellulose derivative to be used according to the invention is incorporated is liquid and contains 10% by weight to 25% by weight, in particular 12% by weight to 22.5% by weight, of nonionic surfactant , 2% by weight to 10% by weight, in particular 2.5% by weight to 8% by weight of synthetic anionic surfactant, 3% by weight to 15% by weight, in particular 4.5% by weight up to 12.5% by weight of soap, 0.5% by weight to 5% by weight, in particular 1% by weight to 4% by weight of organic builders, in particular polycarboxylate such as citrate, up to 1.5% by weight %, in particular 0.1% to 1% by weight of complexing agents for heavy metals, such as phosphonate, and optionally enzyme, Enzyme stabilizer, coloring and / or fragrance as well as water and / or water-miscible solvent.

Solid agents are preferably prepared in such a way that a tissue containing cellulose derivative which is capable of removing dirt is mixed with other detergent ingredients present in solid form. A spray drying step is preferably used to produce the tissue containing the cellulose derivative which is capable of removing dirt. Alternatively, it is also possible to use a compacting compounding step to manufacture this particle and, if appropriate, also to manufacture the finished agent.

example

After washing 5 times with a soil detergent-free Ceululose derivative universal detergent (UWM) or with the otherwise identical detergent, to which 0.5% by weight methyl-hydroxyethyl cellulose (DS 1.89; MS 0.15; average molecular weight 100,000) had been added (UWM + C) at 40 ° C, the following absorbency results for polyester microfiber and a cotton-polyester blend (50% CO / 50% PES) specified in the following table were achieved with hooves of the climbing height test according to DIN 53924:

Claims

claims

1. Use of dirt-free cellulose derivative, which is obtained by alkylation and hydroxyalkyirang of cellulose, to increase the water absorption capacity of textiles made of synthetic material.

2. Use according spoke 1, characterized in that the dirt-releasing cellulose derivative is alkylated with Ci- to Cio groups, in particular Ci- to C ₃ groups, and additionally C ₂ - to Cio-hydroxyalkyl groups, in particular C ₂ - to C ₃ - Hydroxyalkyl groups.

3. Use according spoke 1 or 2, characterized in that in the dirt-releasing cellulose derivative averaged 0.5 to 2.5, in particular 1 to 2 alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3, hydroxyalkyl groups per anhydroglycosomer monomer unit are included.

4. Use according to one of claims 1 to 3, characterized in that the average molecular weight of the dirt-releasing ceululose derivative is in the range from 10,000 D to 150,000 D, in particular from 40,000 D to 120,000 D.

5. Use according to one of claims 1 to 4, characterized in that it takes place in the course of a washing and / or laundry post-treatment step.

6. Use according spoke 5, characterized in that the dirt-releasing cellulose derivative is used as a constituent of a washing or laundry aftertreatment agent which, in addition to the cellulose derivative, has at least one further ingredient selected from enzymatic active ingredients, in particular proteases and lipases, water-insoluble inorganic brothers, water-soluble inorganic and organic builders, in particular based on oxidized carbohydrates, bleaching agents based on peroxygen, in particular alkali percarbonate, synthetic anionic surfactants of the sulfate and sulfonate type, graying inhibitors, in particular anionic cellulose ethers, and laundry softening materials, in particular ester quats.

7. Use according to one of claims 1 to 6, characterized in that the textiles consist of or contain polyester, polyamide, polyacrylonitrile, elastane or mixtures thereof.

8. A method of increasing the water absorbency of textiles made of synthetic material by washing and / or post-treating the textile in the presence of dirt-depleting ceululose derivative obtained by alkylation and hydroxyalkylation of cellulose.